Poly-unsaturated acyclic di-ethers



United States 2,861,109 POLY-UNSATURATED ACYCLIC DI-ETHERS August Sturzenegger, Clifton, N. J., assignor to Hotfmann- La Roche Inc., Nutley, N. J., a corporation of New Jersey No Drawing". Application December 11, 1956 Serial No. 627,571 Claims. (Cl. 260-615) (I) CH3 CH3 R omb=o11*oliroflrd-o-orho m A. 2 CH2 1'14 wherein R represents a member selected from the group consisting of hydrogen and lower alkyl radicals, R represents the ethinyl radical, R represents a lower alkyl radical, and R represents a member selected from the group consisting of hydrogen and lower alkyl radicals.

One general process of making compounds represented by the above Formula I comprises condensing a com pound having the formula wherein R represents a member selected from the group consisting of hydrogen and lower alkyl radicals, and R represents the ethinyl radical,

with a compound having the formula (III) R O-'-CI-I=CHR wherein R represents a lower alkyl radical, and R represents a member selected from the group consisting of.

hydrogen and lower alkyl radicals,

in the presence of an acidic condensing agent. Suitable acidic condensing agents include p-toluenesulfonic acid and boron tri-fluoride; other equivalent acidic condensation agents can be employed. The condensation reaction is conveniently effected by mixing Compound II with Compound ill in the presence of the acidic condensing agent. The reaction is exothermic, and it is ordinarily desirable to cool the reaction mixture so that the temperature of the reaction does not exceed room temperature; preferably, reaction temperatures between about 0 C. and about C. are employed. An inert diluent, preferably a solvent for both reactants, can be employed if desired; but its use is not mandatory. The inclusion of stabilizing agents in the reaction mixture is also optional.

The novel products of the invention represented by the above Formula I are useful as odor-imparting materials in the preparation of perfumes and of scented compositions generally. These compounds of the invention possess characteristic pleasant odors, which can be characterized generally as being reminiscent of cardamon and hydroxycitronellal.

The invention includes compounds which can be designated by the nomenclature: l-(lower alkoxy)-1-(higher alkenynyloxy)-lower alkane. Particularly preferred within this subgenus are those products made by condensing a higher 6-a1ken-1-yn-3-o1 (e, g. 3,7-dimethy1-6-octen-1- atent 0 2,861,109 Patented Nov. 18, 1955 To 76 g. 0 .5 m v of 3,7-dirnethyl-6 octen-l-yn-Seol was'added 10 mg. of p-toluenesulfonic acid, and also. 5

mg. of 2,5-di-(tert.-butyl) hydroquinone as stabilizer. ,.,T6

- scribed in that example.

this mixture was rapidly added, while stirring, 36 g. (0.5 mol) of ethyl vinyl ether. The reaction mixture was stirred for three hours,whi1e cooling to maintainthe temperature between 5 and 10. Then 300. ml. of petroleum ether was added, and the p-toluenesulfonic acid was neutralized by careful addition of sodium methoxide. The mixture was washed twice, each time with 200 ml. of water, dried over anhydrous sodium sulfate; and then was fractionated under reduced pressure. The product, 1 ethoxy-l-(3,7-dimethyl-6-octen-1-yn-3-yloxy)ethane, was obtained in a fraction having B. P. 71-73/ 0.5 mm. and n =1.4466 1.4478.

Example 2 34.8 g. (0.6 mol) of liquefied methyl vinyl ether was added rapidly toa-stirred mixture of 91.2 g. (0.6 mol) of 3,7-dimethyl-6-octem1-yn-3-ol and 7 mg. of p-toluenesulfonic acid, previously cooled to a temperature of minus 15". The mixture was stirredfor four hours while maintaining the temperature between minus 10 and 0. Then 300ml. of diethyl ether was-added and the p-toluenesulfonic acid was neutralized with sodium methoiiide. The reaction mixture was washed twice, each time with 200 ml. of water, the diethyl ether was flashed off, and the residue .was fractionated under reduced pressure. j There was thus obtained l-methoxy-1-(3,7-dimethy1-6-octen-1- yn-3-yloxy)-ethane, B. P.'72 -74/.1.3 mm.,

Example 3 50 g. (0.5 mol) of isobutyl vinyl ether and 76 g. (0.5 mol) of 3,7-dimethyl-6-octen-1-yn-3-ol were reacted in thepresence of 30 mg. of p-toluenesulfonic acid,i'n.tl1e manner described in Example 2, and worked up asfdee There was thus obtained 1- isobutoxy-1-( 3,7 dimethyl-6-octen-1-yn-3-yloxy)-ethane, having B. P. -98/ 1.6 mm., n =1.4450-1.4455.

Example 4 In similar manner to Example 3, by condensing half gram-molar quantities of ether and alcohol, there was obtained, from ethylvinyl ether and 3,7-dimethyl-6- nonen-1-yn-3-ol i l-ethoxy-1-(3,7-dimethyl-6-nonen-1-yn1 3-yloxy)-etha'ne, having B. P. 87-90/1.2 mm.,

n 25=1'.4499- 1.450 6. The-starting material, 3,7-dimethyl-' 6-nonen-1-yn-3-ol, can be made, for example, by the following method:

600 g. of 3-methy1-1-penten-3-ol was cooled to i i-15 with an ice bath, then 1800 ml. of concentrated aqueous hydrochloric acid (containing 37% by weight HCl) was poured into the reaction vessel. The mixture was stirred for 30 minutes. The oil, comprising essentially l-chloro- 3,-methyl-2-pentene, was separated, .washed three times with 500 m1. of water and dried over calcium chloride.

'Four liters of benzene, 1040 g. of ethyl acetoacetate and 378 g. of sodium methylate were stirred into a 12 liter flask. .696 g. of 1-chloro-3-methyl-2-pentene as produced in the preceding paragraph was added from a separatory funnel in two hours at 60. The stirring was then continued at 60 overnight.

The mixture was diluted with four liters of water. The oil was separated and thebenzene was distilled off under racuum. The thick residue, 3-carbethoxy-6-methyl-5- octen-Z-one, was placed in a liter flask with -2 liters of ethyl alcohol, 1 liter of water and 500 grams of potastium h drox de. s s rr f r tw hours, t allowed to set overnight, thereby forming the potassium salt of .3=carhoxy16-methyl-5-octen-2-one.

Concentrated hydrochloric acid was added to the stirred reaction mixture from a separatory funnel until strongly acid. The oil layer was removed, and the aqueous portion was extracted with one liter of benzene. The combined oils were water washed and fractionated to yield :6-methy115-octen 2-one, distilling at 65 mm.,

8.4 g. of metallic sodium was dissolved in 3 liters or liquid ammonia. Acetylene was bubbled into the stirred solutionuntil its color changed from blue to white. 420 g. of G-methyl-S-octen-Z-one was dissolved in 500 ml. of diethyl ether and dropped into the stirred reaction mixture in one hour. Stirring was then continued for three hours while a-slow stream of acetylene was bubbled in. The acetylene was then stopped, butthe stirring was continued for about hours. The ammonia was then distilled ofi and. the residue in the reaction vessel was washed with 2 liters of 5% aqueous sulfuric acid. The product was then water washed, dried over anhydrous calcium sulfate and fractionated to yield 3,7-dimethyl-6-nonen-1-yn-3-ol, distilling at 89 /10 mm., n =-1.-4612.

amp e 6 taining 37% by weight HCl) at room temperature for minutes. The oil layer was separated, washed twice, each time. with 500 ml. of water, and dried over calcium chloride. The product obtained, l-chloro-3,5-dimethyl-2- hexene, had n =1.448.

- In afive-liter flask there was placed 3 liters of benzene, 429 g of ;ethyl acetoacetate and 162 g. of sodium methylate. 428 g. of the product of the preceding paragraph, 1-chloro-3,5rdimethyl-2-hexene, was added at 60 within 30 minutes, and stirring was continuedforsix hours at 60-70. The reaction mixture was washed with 2 liters of water and the benzene was distilled off under a vacuum of 100 mm. to yield 3 -carbethoxy 6,8-dimethyl- S nonen-Z-one as astraw-colored oil.

' The entire quantity of 3-carbethoxy-G,8-dimethyl 5- noneln-Z one produced abovewas dissolved in 2 ,l'itersof. ethyl alcohol. To, this was added 200 g, of s'olidpostassiurn hydroxide and 200 ml. of water. The mixture was stirred for four hours at 40-50 To the resulting solution of the potassium salt of 3-carboxy-6,8-dimethyl-5- nonen-Z-one was then added concentrated aqueoushydromore acid (containing 37% by weight HCl) from a separatory funnel until the solution was strongly and Thirty minutes were required for the addition. The solution was then stirred an additional hour at 50.

The reaction mixture was diluted with 2 liters of water and the oil layer was removed by means of a separatory funnel. The aqueous portion was extracted with500 ml. of benzene. The combined oils were washed neutral with water and fractionated. The product 6,8-dimethyl-5- nonen-Z-one distilled at 120"/ 35 mm., n =1.443-2.

In 1.5 liters of liquid ammonia there was dissolved 41.4 g. of metallic sodium. Acetylene gas was passed into the blue colored solution, until the color changed to white. The addition of acetylene was continued for an extra 30 minutes. Then a solution of 252 grams of 6,8-dimethyl- 5-nonen-2-one, dissolved in 250 ml. of ethyl ether, was dropped in within 45 minutes. The stirring was continued for 15 hours while a slow stream of acetylene was bubbled into the reaction mixture. The ammonia was thereupon evaporated from the reaction mixture with the aid of a slow stream of nitrogen. The residue'was poured into two liters of 5% sulfuric acid. The oil layer was removed and washed neutral with water. On fractionation, 3,7,9-trimethyl-6-decen-1-yn-3-ol was obtained in a fraction distilling at 72/0.35 mm., rz =1.4598.

Example 7 To 91.2 g. of 3,7-dimethyl-6-octen-1-yn-3-ol was added 10 mg. of p-toluenesulfonic acid. The mixture was cooled to 0, and while stirring, 51.7 g. of ethyl l-propenyl ether was added rapidly. The mixture was stirred for four hours at 0 to 10, and was then diluted with 300 ml. of diethyl ether. The catalyst was neutralized by careful addition of sodium methoxide. Then the reaction mixture was washed to neutrality with two 200 ml. portions of water. The solvent was flashed oh and the residue was fractionated under reduced pressure. The product, 1-ethoxy-1-(3,7-dimethyl-6-octen-l-yn-3-yloxy)- propane, was obtained in a fraction having B. P. 86/ 1.0 mm., n =1.44711.4472.

I claim:

1. A compound having the formula CH CH BJ-CHz( J=CIE[CHn-CHlq(i1-O-GHOR wherein R represents a member selected from the group consisting of hydrogen and lower alkyl radicals, R represents the ethinyl radical, R represents a lower alkyl radical, and R represents a member selected from the group consisting of hydrogen and lower alkyl radicals.

2. l-(lower alkoxy)-l-(3,7 dimethyl-6-octen-1-yn-3- yloxy) -ethane.

3. l-(lower alkoxy)-1-(3,7-dimethyl-6-nonen-1-yn-3- yloxy)-ethane. 1

4. l-(lower alkoxy)-19(3,7,9-trimethyl-6-decen-1-yn-3- yloxy) -ethane.

5. l-(lower alkoxy)-1-(3,7 dimethyl-6-octen-l-yn-3- yloxy) -propane.

References Cited in the tile of this patent UNITED STATES PATENTS Groll et al. May 26, 1936 Mikeska et al Aug. 19, 1941 OTHER REFERENCES 

1. A COMPOUND HAVING THE FORMULA 